Process for dimerization of alpha-olefins

ABSTRACT

PROCESS OF CATALYTIC DIMERIZATION OR CO-DIMERIZATION OF A-OLEFINS COMPRISING ETHYLENE AND/OR PROPYLENE IN THE PRESENCE OF THE COMPLEX CATALYST CONSISNTING OF ORGANOALUMINUM COMPOUNDS AND AT LEAST ONE OF TITANATES SELECTED FROM THE GROUP CONSISTING OF TRI-ALKYLTITANATES AND TETRAARYLTITANATES(E.G. TETRA-PHENYLTINATES AND/OR TETRA-TOLYLTITANATE ET AL.).

United States Patent Ofice 3,564,071 PROCESS FOR DIMERIZATION OFa-OLEFINS Shoichi Izawa, Shizuo Yamada, and Yaichiro Ono, Yamaguchi-ken,Japan, assignors to Toyo Soda Manufacturing Co., Ltd., Yamaguchi-ken,Japan No Drawing. Filed Oct. 11, 1968, Ser. No. 766,969 Claims priority,application Japan, Oct. 19, 1967, 42/ 67,333 Int. Cl. C07c 3/10 US. Cl.260-683-15 12 Claims ABSTRACT OF THE DISCLOSURE Process of catalyticdimerization or co-dimerization of u-olefins comprising ethylene and/orpropylene in the presence of the complex catalyst consisting oforganoaluminum compounds and at least one of titanates selected from thegroup consisting of tri-alkyltitanates and tetraaryltitanates (e.g.tetra-phenyltitanates and/or tetra-tolyltitanate et al.).

BACKGROUND OF INVENTION Among n-butenes, 1-bntene having a terminaldouble bond is the important materials to produce poly-l-butene. Atpresent, it is considered that B-B fraction from petroleum refineryplants is the source of l-butene, however, besides l-butene the said B-Bfraction usually contain cis- 2-butene, trans-2-butene, n-butene, andbutadiene and the contents of l-butene are reported in the range of17-20 percent.

To separate l-butene from B-B fraction is very tedious because theboiling points are very close to each other, so that it is notappropriate to ask for the B-B fractions as a source of l-butene fromeconomic point of view.

Poly-l-butene (i.e. polymers of l-butene) have numerous excellentproperties compared with polyethylene and polypropylene and used asreforming materials of polyethylene.

The said poly-l-butene are not yet present in the market because of thesituations for supplying raw materials. Industrially, it is importantand most desired to supply l-butene at low cost.

Further, ot-olefins having 5 to 6 carbon atoms in the molecules areconsidered as important raw materials for producing intermediatecompounds of plastic and synthetic rubber as described later.

Hitherto, numerous processes for preparation of nbutene are described inthe literature and it is very difficult to obtain l-butene selectivelybecause these butenes comprises isomers having analogous boiling points.Especially, the process for preparation of n-butene by dimeri- Zation ofethylene have been disclosed in numerous patents and in many cases,these processes have some disadvantages (e.g. low activity, lowselectivity of l-butene, need of high temperature and pressure). Up tonow, the process for dimerization of ethylene to produce l-butene arenot yet securely established industrially. For example, according to theprocess of Japanese patent publication No.

5,067/ 1957, the mixture of triethylaluminum and tetrabutyltitanate ortetrabutylzirconate are employed as polymerization catalyst and ethyleneis used as a raw materials for preparing mainly n-butene and smallamounts 3,564,071 Patented Feb. 16, 1971 of hexene and its homologues.Example 1 in the said process is reviewed as follows.

mmol.) l-butene (g.)/titanate (g.) reaction time (hrs.): 108/8.541=0.31.

These values are insufficient as industrial catalysts.

Relating to the co-dimerization of ethylene and propylene, there havebeen tried a number of research and development for the purpose toobtain isoprene as the material for synthetic polyisoprene rubber andmonomer of poly(3-methyl-l-butene) which has various characteristics asa new polymer, which has resulted in many patents. They are, forexample, Japanese patent publication No. 2662/1959, Japanese patentpublication No. 9,058/ 1962 and French Pat. No. 1,385,503. However, theyare proved to have ditficulties in that reaction conditions are severe,yields of reaction product are low, or unnecessary reaction products areby-produced. This actually means that it has not yet come to a stage ofthe establishment of a firm technology available for a commercialoperation of the co-dimerization of ethylene and propylene.

Therefore, the current situation is that it has been desired toestablish a process to produce these 3-methyl-1- butene,2-methyl-2-butene and 2- methyl-l-butene etc. at a low cost.

Relating to the co-dimerization of propylene, considerable research anddevelopment have been made to obtain the monomer for the synthesis ofpoly(4methyl-1-pentene), Z-methyl-l-pentene and 2-methyl-2-pentene torthe synthesis of isoprene, which has resulted in many patents. They are,for example, French Pat. No. 1,385,503, Japanese patent publications No.14,367/ 1960, No. 19,622/ 1964 and No. 20,249/ 1965. However, they areproved to have difliculties in a scale of commercial operation.Therefore, it has been desired to establish a process for the synthesisof these materials important for industries.

As the results of our researches, the new catalyst system fordimerization of ethylene or propylene, and codimerization ofethylene-propylene are discovered. Using these catalyst systems, thedimerization of ethylene was carried out somewhat quickly at ordinarytemperature and pressure and hexenes in the products were relativelysmall and, further, the contents of l-butene having a terminal doublebond, was 99 percent or more among produced butenes. Then, thesecatalyst systems are also effective for dimerization of propylene andco-dimerization of ethylene-propylene, and these dimers and co-dimerscontains 3-methyl-1-butene, Z-methyl-l-butene, 4-methyl-1- pentene andetc., having a terminal double bond selectively.

DETAILED DESCRIPTION OF INVENTION In accordance with the presentinvention, the mixture of organoaluminum compounds (Compound A) and atleast one of titanates selected from the group consisting oftri-alkyltitanates and tetraaryltitanates (Compound B) alone or in theappropriate solvents may be used as cata- 3 lyst and dimerization ofethylene or propylene, or codimerization of ethylene and propylene maybe carried by contacting the catalyst with ethylene, propylene, ormixture gas of ethylene-propylene at ordinary temperature or up to 150C. and under atmospheric pressure or increased pressure.

Of our catalyst systems, the organoaluminum compounds (compound A) havea bond of aluminum atom and organic carbon atom in molecules and can berepresented by the general formula R Al or R AlH, wherein R is an alkylgroup having 2 to 6 carbon atoms and trialkyltitonates ortetraaryltitanates (compound B) can be represented by the generalformula of Ti(OR) wherein R is an alkyl group having 2 to 4 carbonatoms, or Ti(OAr) wherein Ar an aryl group or its derivatives which areexpressed by -C H et al. These were prepared by the method ofNesmeyanov, Nogina and Freidlina (CA. 50, 15413) or Yoshino et al. (T.Yoshino: Kogyo Kagaku Zasshi; 60 1124-25 (S7) J. Chem. Soc. Japan; Ind.Chem. Sect.)

Further, the compounds A and B are not defined limitedly as each onekind and if necessary, two kinds or more of compounds may be mixed andused as the said component A or B and these are comprised in category ofthe present invention. According to the present invention, the catalystof two components which is obtained by making compounds A to contactwith compound B, shows superior activity and a molar ratio of componentA to B (A/ B) shall be suitable within the range of from 1.0 to 5.0. Ifthe value of A/ B was smaller than 1.0, the formation of catalyst is notsmoothly carried out and the catalyst exerts low activity. If the valueA/B was over 5.0, the secondary reactions e.g. formation of solidmaterials having molecular weight and the like, is caused and the yieldof dimers are lowered. As for the concentration of catalyst, thecatalyst solutions which contains 3 mmol/l. or more of titanate issatisfactory used. In this case, if the concentration of catalyst was 3mmol/l. or less, the activity of catalysts is weakened or lost byimpurity in solvents and the reproducibility of dimerization is rapidlydecreased.

Further, the reaction of ethylene proceed at a temperature of from 0 C.to 100 C. and if the reaction temperature was lower than 0 C. thereaction rate is decreased, on the ther hand, if the reactiontemperature was higher than 100 C., the activity of catalyst is notshown so much by decomposition of catalyst system so that it wasdisclosed that a suitable temperature exists in the range of from 30 C.to 60 C., and the reaction of propylene or ethylene-propylene mixtureproceed at the range of from 0 C. to 150 C., preferably from 60 C. to 80C.

As for the solvents, aliphatic, aromatic, and alicyclic hydrocarbon(such as n-heptane, toluene, and cyclohexane) may be employed. Then areaction may proceed at atmospheric pressure or increased pressure andthe reaction rate increases with pressure.

The following examples will more particularly illustrate the novelprocess of this invention, however, it is to be understood that theexamples are for the purpose of illustration only and are not intendedto define or limit the scope of the invention.

Example I The catalyst was prepared in 200 ml. autoclave withelectromagnetic stirrer in a nitrogen filled dry box. 4 ml. of n-heptanecontaining 1.6 mmol of triethylaluminum was added to 0.54 mmol (0.2280g.) of tetraphenyltitanate, then n-heptane was further added so as to atotal volume may reach to 80 ml. The catalyst solution thus obtained wasmatured at 40 C. for 10 mins. and to which ethylene was introduced up tokg./cm. G. and then the reaction was carried out at the same temperatureand pressure for 40 mins. After the reaction the autoclave was cooled ata temperature of 30 C. and the products in the reaction vessel weredischarged through the trap which was cooled with solid carbondioxide-methanol solutions. Further the reaction solution was heated anda product having low boiling point which contains namely n-butene wascollected in the same trap. Then another product having high boilingpoint which contained hexene in the reaction solution was separated bydistillation. These were respectively analyzed by means ofgaschromatography. The solid products were washed with hydrochloricmethanol solution and then dried. Thus 19.4 g. of n-butenes (l-butene;99.8 percent), 1.2 g. of hexene, and 0.6 g. of solid polymer wereobtained. Here, the amounts of l-butene produced per gram of titanatewas calculated as below.

19.4 g./0.2280 g.=85.l (l-butene g./g. titanate) This value will beexpressed as X in the following examples. For the next, theratio ofl-butene, hexene, and polymer among reaction products were 91.5, 5.6 and2.9 percent respectively.

Example II The following were mixed in an inert atmosphere in theautoclave as described in Example I; 0.53 mmol (0.221 g.) oftetraphenyltitanate and 1.58 mmol of triethylaluminum in ml. n-heptane.Ethylene was then introduced at a pressure of 20 l g./cm. at G. at 80 C.for 1 hr. As the results of the reaction, 13.3 g. of n-butene (l-butene;99.8 percent), 1.9 g. of hexene, and 0.1 g. of solid polymer wereobtained and the value of X was 60.2.

Example III As described in Example I; to 80 ml. of n-heptane solutioncontaining 0.56 mmol (0.2371 g.) of tetraphenyltitanate and 1.75 mmol oftriisobutylaluminum, ethylene was introduced at a pressure of 30 kg./cm.G. at 30 C. for one hour. Thus, 25 g. of n-butene (l-butene; 99.6percent), 1.7 g. of hexene and 1.4 g. of solid polymer were obtained andthe value of X was calculated at 105.4.

Example IV As described in Example I; ethylene was introduced to 80 ml.of toluene solution containing 0.5 mmol (0.2100 g.) oftetraphenyltitanate and 1.5 mmol of triethylaluminum at a pressure of 20kg./cm. G. at 0 C. for one hour. Thus, 7.9 g. of n-butene (l-butene;99.7 percent), 0.3 g. of hexene, and 0.4 g. of solid polymer wereobtained. The value of X was calculated at 37.6.

Example V As described in Example I; ethylene was introduced to 80 ml.of catalyst solution (cyclohexane was employed as solvents) containing1.6 mmol (0.6840 g.) of tetraphenyltitanate and 8.1 mmol ofdiisobutylaluminum hydride at a pressure of 15 kg./crn. G. at 30 C. forone hour. Thus, 12.1 g. of n-butene (l-butene; 99.3 percent), 0.7 g. ofhexene and 3.5 g. of solid polymer were obtained. The ratio of n-butene,hexene, and solid polymer among reaction products, were 74.5, 4.0 and21.5 percent respectively. The value of X was 17.7.

Example VI As described in Example I; ethylene was introduced to 80 ml.of catalyst solution containing 0.25 mmol (0.1035 g.) oftetraphenyltitanate and 0.98 mmol of triethylaluminum at a pressure of15 l g./cm. G. at 60 C. for one hour. Thus, 19.4 g. of n-butene(l-butene; 99.8 percent), 1.4 g. of hexene and 0.2 g. of solid polymerwere obtained and the value of X was calculated at 187.4.

Example VII As described in Example I; ethylene was charged into 80 ml.of n-heptane solution containing 0.89 mmol (0.3750 g.) oftetraphenyltitanate and 0.9 mmol of triethylaluminum at atmosphericpressure at 30 C. for 2 hrs. Thus 20 g. of n-butene (l-butene; 99.9percent), a small amount of hexene, and solid polymer were obtained.

Example VIII As described in Example I; ethylene was introduced to 80ml. of catalyst solution containing 0.53 mmol (0.2213 g.) oftetraphenyltitanate and 1.6 mmol of triethylaluminum at a pressure of 15kg./cm. G. at 30 C. for 6 hrs. Thus 32.4 g. of n-butene (l-butene; 99.8percent), 2.0 g. of hexene, and 1.2 g. of solid polymer were obtainedand the value of X was 146.4.

Example IX As described in Example I; ethylene was introduced to 80 ml.of n-heptane solution containing 0.53 mmol (0.2227 g.) oftetraphenyltitanate and 1.59 mmol of triethylaluminum at the pressure of20 kg./cm. G. at 60 C. for one hour. Thus 54.7 g. of n-butene (l butene;99.8 percent), 5.0 g. of hexene and 0.8 g. of solid polymer wereobtained and the value of X was calculated at 245.6.

Example X As described in Example I; ethylene was introduced to 80 ml.of n-heptane solution containing 0.58 mmol of tetra-p-tolyltitanate[Ti(O--C H.,CH 0.2770 g.] and 1.74 mmol of triethylaluminum at thepressure of 15 kg./ cm? G. at 40 C. for 40 mins. Thus 20.6 g. ofn-butene (l-butene; 99.8 percent), 1.3 g. of hexene, and 0.7 g. of solidpolymer were obtained and the value of X was calculated at 74.4.

Example XI The procedure was as described in Example X; except that thetetra-p-tolyltitanate and triethylaluminum are replaced by 0.55 mmol oftetra o tolyltitanate [Ti(O-C H -CH 0.2630 g.] and 2.8 mmol oftrihexyl-aluminum. As the results, 9.1 g. of n-butene (1- butene; 99.1percent), 0.8 g. of hexene, and 1.6 g. of

solid polymer were obtained and the value of X was 34.6.

Example XII As described in Example I; ethylene was introduced to 80 ml.of n-heptane solution containing 0.59 mmol oftetra-p-chlorophenyltitanate [Ti(OC H Cl) 0.3326 g.] and 1.79 mmol oftri-n-propylaluminum at a pressure of 15 kg./cm. G. at 40 C. for 40mins. As the result, 13.3 g. of n-butene (l-butene; 99.6 percent), 0.9g. of hexene, and 1.4 g. of solid polymer were obtained and the value ofX was calculated at 40.0.

Example XIII As described in Example I; ethylene was introduced to 80ml. of n-heptane solution containing 0.59 mmol oftetra-o-chlorophenyl-titanate [Ti(OC ,-H Cl) 0.3310 g.] and 3.0 mmol oftri-n-butylaluminum at a pressure of 15 kg./cm. G. at 40 C. for 40 mins.Thus, 8.1 g. of nbutene (l-butene; 99.7 percent), 1.1 g. of solidpolymer, and the small amounts of hexene were obtained.

Example XIV As described in Example I; ethylene was introduced to 80 ml.of n-heptane solution containing of 0.58 mmol oftetra-p-nitrophenyltitanate [Ti(OC H NO 0.3515 g.] and 2.9 mmol oftriethylaluminum at a pressure of 15 kg./cm. G. at 40 C. for 40 mins.Thus, 1 g. of nbutene, 4.8 g. of solid polymer, and the small amounts ofhexene were obtained.

Example XV As described in Example I; ethylene was introduced into 80ml. of n-heptane solution containing 0.56 mmol of tetra-m-tolyltitanate[Ti(OC H CH 0.267 g.] and 1.8 mmol of triethylaluminum at a pressure of15 kg./cm. G. at 40 C. for 40 mins. Thus, 13.8 g. of n-butene (1-butene, 99.8%), 1.2 g. of hexene, and 0.9 g. of solid polymer wereobtained.

6 Example XVI The procedure is as described in Example XV; except that1.8 mmol of triethylaluminum is replaced by 2.8 mmol oftriethylaluminum. As the results, 6.0 g. of nbutene (l-butene; 99.8% 0.6g. of hexene, and 3.0 g. of solid polymer were obtained.

Example XVII As described in Example I; ethylene was introduced into 80ml. of n-heptane solution containing 0.844 mmol of tetra ptert-butylphenyltitanate [Ti(0C H C H 0.544 g.] and 4.22 mmol oftriethylaluminum at a pressure of 15 kg./cm. G. at 40 C. for 40 mins.Thus, 51.8 g. of n-butene (l-butene; 99.7%), 9.1 g. of hexene and 0.7 g.of solid polymer were obtained and the value of X was 95.2.

Example XVIII As described in Example I; ethylene was introduced into 80ml. of n-heptane solution containing 0.612 mmol of tetra ptert-amylphenyltitanate [Ti(OC H C H 0.429 g.] and 3.06 mmol oftriethylaluminum at a pressure of 10 kg/cm? G. at C. for one hour. Thus,28.8 g. of n-butene (99.4% of l-butene), 6.1 g. of hexene and 1.0 g. ofsolid polymer. Thus the value of X was 67.1.

Example XIX As described in Example I; ethylene was introduced into thesolution of n-heptane containing 0.568 mmol of tetra pphenylphenyltitanate [Ti(OC H C H 0.4118 g.] and 2.84 mmol oftriethylaluminum at a pressure of 10 l g./cm. G. at 75 C. for one hour.Thus, 23.4 g. of n-butene (l-butene; 99.4%), 4.3 g. of hexene and 0.1 g.of solid polymer were obtained and the value of X was calculated at56.8.

Example XX As described in Example I; ethylene was introduced into ml.of n-heptane solution containing 0.570 mmol of tetra-3,4-dimethylphenyltitanate [Ti{OC H (CH 0.3036 g.] and 2.28 mmol of triethylaluminumat a pressure of 10 kg./cm. G. at 75 C. for one hour. Thus, 19.1 g. ofn-butene (l-butcne; 99.5%), 3.1 g. of hexene and 1 g. 22f 9solid polymerwere obtained and the value of X was Example XXI Example XXII Asdescribed in Example I; ethylene was introduced into 80 ml. of n-heptanesolution containing 1.56 mmol of tri-n-butoxytitanium (0.42 g.) and 7.8mmol of triethylaluminum at a pressure of 15 kg./cm. G. for 2 hrs. Thus,1 g. of n-butene (l-butene; 98.1%), 0.1 g. of hexene and 5.0 g. of solidpolymer were obtained.

Example XXIII The catalyst was prepared in ml. stainless ampoule in anitrogen filled dry box. 40 ml. of n-heptane containing 0.38 mmol oftri-n-butoxytitanium (0.1 g.) and triisobutylaluminum was niaturld at 30C. for 10 mins. and to which ethylene was introduced up to 15 kg./cm. G.and then reaction was carried out for one hour. Thus, 1.2 g. of butenecontaining 99% of l-butene, a small amount of hexene and solid polymerwere obtained.

7 Example XXIV As described in Example XXIII; ethylene was contactedwith 40 ml. of catalyst solution containing 0.41 mmol oftri-n-proproxytitanium (0.092 g.) and 9.81 mmol of diisobutylaluminumhydride, and reaction was carried out at a pressure of 15 kg./cm. G. at85G for 2 hrs. Thus, 1.5 g. of n-butene (l-butene; 99.0%), a smallamount of hexane, and solid polymer were obtained.

Example XXV As described in Example XXIII; to 40 ml. of n-heptanesolution containing of 0.35 mmol of tri-ethoxytitanium (0.64 g.) and 0.7mmol of tripropylaluminum, ethylene was introduced at a pressure of 55kg./cm. G. at 30 C. for 2 hrs. Thus, 4 g. of n-butene (l-butene; 99.8%),0.15 g. of hexane and 0.1 g. of solid polymer were obtained and thevalue of X was calculated at 105.4.

Example XXVI As described in Example XXIII; ethylene was introduced to40 ml. of n-heptane solution containing 0.36 mmol oftri-n-butoxytitanium (0.097 g.) and 0.73 mmol of triethylaluminum at apressure of 15 kg./cm. G. at C. for 2 hrs. Thus, 1 g. of n-butene(l-butene; 99%), a small amount of hexene, and solid polymer wereobtained.

Example XXVII As described in Example I; ethylene was introduced to 80ml. of n-heptane solution containing 0.79 mmol of tri-n-butoxytitanium(0.211 g.) and 2.37 mmol of triethylaluminum at a pressure of kg./cm. G.at 30 C. for 3.5 hrs. Thus, 33.9 g. of butene (l-butene; 99.6% 4.2 g. ofhexene, and 2.0 g. of solid polymer were obtained. The value of X wascalculated at 160.6. The ratio of n-butene, hexene and solid polymeramong reaction products were 84.8, 10.5 and 4.7 percent respectively.

Example XXV III The following were mixed in 200 ml. autoclave; 0.97 mmol(0.4627 g.) of tetraphenyltitanate, and 2 ml. of n-heptane containing2.9 mmol of triethylaluminum and 50 ml. of n-heptane, and then 35 g. ofpropylene were introduced into the said autoclave. The pressure in theautoclave showed 16 kg./cm. G. as it was kept at 60 C. and then ethylenewas introduced into the reaction system at a pressure of 18 kg./cm. G.at 60 for 2 hrs. After 2 hrs., the products in the autoclave werecollected in a cooling trap and the products having high boiling pointswere separated by distillations. These products were analysed bygas-chromatography and the following results were obtained. It wasobtained that 3.7 g. of n-butenes (l-butene; 99%), 3.4 g. of pentenes(3- methyl-l-butene; 28%, 2-rnethyl-1-butene; 72%), and 0.6 g. of hexene(4-methyl-1-pentene; 20.5%, 4-methyl- 2-pentene; 47.5%,Z-methyl-l-pentene; 14.4%, 2-ethyl-lbutene; 10.0% and 7.4% of unknownmaterials).

Example XXIX As described in Example XXVIII; 35 g. of propylene wasadded to 50 ml. of n-heptane solution containing 1.06 mmol (0.5902 g.)of tetra-p-chlorophenyltitanate and 3.2 mmol of triethylaluminum, and atemperature was kept at 40 C., a pressure in the reactor was reached to10 kg./cm. G. Then ethylene was introduced at a pressure of 14 kg./cm.G. at 40 C. for 2 hrs. Thus 4.8 g. of n-butene (98.2% of l-butene, andothers), 2.5 g. of pentene (3-methyl-1-butene; 28%, 2-methyl-1-butene;71.8%, and others), and 0.2 g. of hexene (4-methyl-1- pentene; 18.2%,4-methyl-2-pentene; 52.2%, 2-methyl-1 pentene; 11.3, Z-ethyl-l-butene;12.0%, and others).

Example XXX As described in Example XXVIII; 35 g. of propylene wascharged in 50 ml. of n-heptane solution containing 1.04 mmol (0.4956 g.)of tetra-p-tolyltitanate and 3.2 mmol of triethylaluminum, and as atemperature was kept at 60 C., the pressure in the autoclave was reachedto 16 kg./cm. G., then ethylene was introduced at a pressure of 20kg./cm. G. at 60 C. for 2 hrs. Thus, it was obtained that 2.5 g. ofn-butenes (l-butene; 98.5% and others i.e. 2-butene), 1,4 g. of pentenes(3-methyl-1- butene; 36%, 2-methyl-1-butene; 64%), and 0.4 g. of hexenes(4-methyl-l-pentene; 27%, 4-methyl-2-pentene; 10 15.5%,Z-methyl-l-pentene; 10.9% and 2-cthyl-l-butene;

Example XXXI As described in Example XXVIII; 32 g. of propylene 15 wasadded to 40 ml. of n-heptane solution containing 1.8 mmol (0.47 g.) oftri-n-butoxytitanium and 8.8 mmol of triethylaluminum, and as atemperature was kept at 60 C., a pressure in the reactor was reached to18 kg./ cm. G. Then ethylene was introduced at a pressure of 18 kg./cm.G. at 60 C. for 3.5 hrs. Thus, 3.3 g. of reaction products wereobtained. The ratio of each fraction among above product were 51 wt.percent of nbutenes (l-butene; 88.2%, trans-2-butene; 7.1%, cis-2-butene; 1.1% and others), 44.4 wt. percent of pentenes(3-methyl-1-butene; 32.9%, Z-methyl-l-butene; 32.9%,

Z-methyl-l-butene; 57.5%, and others), and 4.6 wt. percent hexenes(4-methyl-1-pentene; 18.8%, 4-methyl-2- pentene; 31.3%,2-methyl-1-pentene; 12.5%, 2-ethyl-1- butene 25.0% and others).

Example XXXII As described in Example XXVIII, 32 g. of propylene wasadded to 40 ml. of n-heptane solution containing 1.9 mmol (0.51 g.) oftri-n-butoxytitanium and 9.5 mmol of 35 triethylaluminum, and as atemperature was kept at 75 C., a pressure in the reactor was reached to21 kg./crn. G. Then ethylene was introduced at a pressure of 21 kg./cm.G. at 75 C. for 3.5 hrs. Thus, 3 g. of reaction products containing 68.8wt. percent of n-butenes (1- butene; 90.0%, trans-2-butene; 7.8%,cis-Z-butene; 0.5%

and others), 24.6 wt. percent of pentenes (3-methyl-1- butene; 36.0%,2-methyl-1-butene; 57.8%, l-pentene; 3.5% and others), and 6.6 Wt.percent of hexenes (4- methyl-l-pentene; 23.5%, Z-methyl-l-pentene;17.8%, 2- ethyl-l-pentene; 41.2% and 4-methyl-2-pentene; 17.5%) wereobtained.

Example XXXIII As described in Example XXVIII; 30 g. of propylene wascharged in 50 ml. of n-heptane solution containing 1.7 mmol (0.45 g.) oftri-n-butoxytitanium and 17.0 mmol of triethylaluminum, and as atemperature was kept at 110 C., the pressure in the reactor was reachedto 24 kg./cm. G. Then, ethylene was introduced at same pressure and sametemperature for 3.5 hrs. As the results, 2.4 g. of reaction productswere obtained, and these products were composed of 37.5 wt. percent ofn-butenes (l-butene; 39.2 wt. percent, trans-2-butene; 47.8 wt. percent,cis-Z-butene; 5.1 wt. percent, and others), 50.0 wt. percent of pentenes(3-methyl-1-butene; 35.8%, Z-methyI-I-butene; 51.0%, 2-methyl-2-butene;5.7%, 2- pentene; 2.6% and others), and 12.5 wt. percent of hexenes(4-methyl-1-pentene; 18.8%, Z-methyI-I-pentene; 18.8%,4-methyl-2-pentene; 32.0%, 2-ethyl-l-butene; 17.6% and others; 12.8%).

Example XXXIV g. of propylene was charged into ml. of nheptane solutioncontaining 1 mmol (0.42 g.) of tetraphenyltitanate and 2.9 mmol oftriethylaluminum and the reaction was carried out under the pressure of16 kg./cm. G. at C. for 2 hrs. Thus, 0.4 g. of products were obtainedand these hexenes contained 20.6% of 4-methyll-pentene, 44.5% of4-methyl-2-pentene, 12.0% of 2- methyl-l-pentene and others.

9 Example XXXV As described in the Example XXXIV; 35 g. of propylene wascharged into 50 ml. of n-heptane solution containing 0.99 mmol (0.4734g.) of tetra-o-tolyltitanate and 4.97 mmol of triethylaluminum and thereaction was carried out under the pressure of 16 kg./cm. G. at 60 C.for 2 hrs. Thus, 08 g. of reaction products were obtained and thesecontained 0.4 g. of solid polymer and 0.4 g. of hexenes, composition ofwhich were the same as shown in Example XXXIV.

Example XXXVI Example XXXVII As shown in Example XXXIV; 26 g. ofpropylene was charged into 30 ml. of n-heptane solution containing 1.73mmol (0.39 g.) of tri-n-propoxytitanium and 8.7 mmol ofdiisobutylaluminum hydride, and then reaction was carried out at 75 C.for 4 hrs. While in this reaction, the pressure in the reactor decreasedfrom 20 kg./cm. G. to 10 kg./cm. G. Thus, 2 g. of hexenes (4-methyl-1-pentene; 11%, 2-methyl-1-pentene; 25.7%, 4-methyl-2- pentene; 30.3%, andothers) were obtained.

Example XXXVIII As shown in Example XXXIV; 25 g. of propylene wascharged into 40 ml. of n-heptane solution containing 2.6 mmol (0.68 g.)of tri-n-butoxytitanium and 25.6 mmol of triethylaluminum, and thenreaction was carried out at 75 C. for 4 hrs. While in this reaction, thepressure in the reactor decreased from 15 kg./cm. G. to 5 kg./cm. G.Thus, 3 g. of hexenes (4-methyl-1-pentene; 30%, Z-methyl-l-pentene;28.5%, 4-methyl-2-pentene; and others) were obtained.

What is claimed is:

1. Process for the dimerization or co-dimerization of a-olefin having 2to 3 carbon atoms per molecule, which comprises contacting said u-olefinwith a binary catalyst consisting of (A) at least one organic aluminumcompound selected from the group consisting of R A1 and R AlH, wherein Ris an alkyl group having 2 to 6 carbon atoms and (B) at least onetitanate compound selected from the group consisting of Ti(OAr) andTi(OR') wherein Ar is an aryl group and R is an alkyl group having 2 to4 carbon atoms.

2. Process according to claimv 1, in which the molar ratio of saidorganic aluminum compound to said titanate is within the range of from1.0 to 5.0.

3. Process according to claim 1, in which ethylene is dimerized.

4. Process according to claim 3, in which dimerization is carried out atthe temperature range from 0 C. to 100 C.

5. Process according to claim 1, in which propylene is dimerized.

6. Process according to claim 5, in which dimerization is carried out atthe temperature range from 0 C. to C.

7. Process according to claim 1, in which ethylene and propylene areco-dimerized.

8. Process according to claim 7, in which co-dimerization is carried outat the temperature range from 0 C. to 150 C.

9. Process for the dimerization or co-dimerization of an a-olefin having2 to 3 carbon atoms per molecule, which comprises contacting saida-olefin with a binary catalyst consisting of (A) at least onealkyl-aluminum compound selected from the group consisting of R Al and RAlH, wherein R is an alkyl group having 2 to 6 carbon atoms and (B) atleast one titanate selected from the group consisting of Ti(OAr) whereinthe Ar group is selected from the group consisting of phenyl, loweralkyl phenyl, and halophenyl and nitrophenyl, said catalyst containingfrom 1.0 to 5.0 mole of component (A) per mol of component (B).

10. Process for the dimerization or co-dimerization of a-olefin having 2to 3 carbon atoms per molecule, which comprises contacting said u-olefinwith a binary catalyst consisting of (A) at least one organic aluminumcompound selected from the group consisting of R Al and R AlH, wherein Ris an alkyl group containing 2 to 6 carbons atoms and (B) at least onetri-alkoxy-titanium compound selected from the group consisting ofTi(OR) wherein R is an alkyl group having 2 to 4 carbon atoms.

11. Process for dimerization' or co-dimerization of C(- olefins in whichot-olefins having 2 to 3 carbon atoms are contacted with a binarycatalyst consisting of at least one of the organic aluminum compoundsselected from the group consisting of R Al and R AlH, wherein said R isthe alkyl group having 2 to 6 carbon atoms, and at least one of thetitanates selected from the group consisting of Ti(OAr) wherein said Aris the aryl group selected from phenyl, tolyl, chlorophenyl, andnitrophenyl, and having molar ratio of the organic aluminum compound tothe titanate in the range from 1.0 to 5.0.

12. Process for dimerization or co-dimerization of 0&- olefins in whicha-olefins having 2 to 3 carbon atoms are contacted with catalystcomprising at least one organic aluminum compound selected from thegroup consisting of R Al and R AlH, wherein said R is the alkyl grouphaving 2 to 6 carbon atoms, and at least one titanate selected from thegroup consisting of Ti(OR) wherein said R is the alkyl group having 2 to4 carbon atoms, and having molar ratio of the organic aluminum compoundto the titanate in the range from 1.0 to 5.0.

References Cited UNITED STATES PATENTS 2,943,125 6/1960 Ziegler et a1.260683.15 2,959,576 11/1960 Payne 260-93.7X 3,073,811 1/1963 Natta eta1. 26093.7 3,113,986 12/1963 Breslow et al 252429X PAUL M. COUGHLAN,JR., Primary Examiner US. Cl. X.R.

